CN116588941B - Method for comprehensively utilizing yellow phosphorus slag - Google Patents
Method for comprehensively utilizing yellow phosphorus slag Download PDFInfo
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- CN116588941B CN116588941B CN202310573712.1A CN202310573712A CN116588941B CN 116588941 B CN116588941 B CN 116588941B CN 202310573712 A CN202310573712 A CN 202310573712A CN 116588941 B CN116588941 B CN 116588941B
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- yellow phosphorus
- phosphorus slag
- comprehensively utilizing
- metal oxide
- carbon black
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- 239000002893 slag Substances 0.000 title claims abstract description 52
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000007788 liquid Substances 0.000 claims abstract description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000006229 carbon black Substances 0.000 claims abstract description 33
- 239000002131 composite material Substances 0.000 claims abstract description 33
- 239000002699 waste material Substances 0.000 claims abstract description 26
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 25
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 25
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 24
- 239000000047 product Substances 0.000 claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 19
- 238000001354 calcination Methods 0.000 claims abstract description 18
- 238000000227 grinding Methods 0.000 claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 239000002028 Biomass Substances 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 238000000926 separation method Methods 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 13
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims abstract description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 7
- 239000002244 precipitate Substances 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 240000000111 Saccharum officinarum Species 0.000 claims description 9
- 235000007201 Saccharum officinarum Nutrition 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 5
- 235000017060 Arachis glabrata Nutrition 0.000 claims description 4
- 244000105624 Arachis hypogaea Species 0.000 claims description 4
- 235000010777 Arachis hypogaea Nutrition 0.000 claims description 4
- 235000018262 Arachis monticola Nutrition 0.000 claims description 4
- 240000008042 Zea mays Species 0.000 claims description 4
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 4
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 4
- 235000005822 corn Nutrition 0.000 claims description 4
- 235000020232 peanut Nutrition 0.000 claims description 4
- 239000002023 wood Substances 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 2
- 239000000618 nitrogen fertilizer Substances 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 4
- 239000002910 solid waste Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000012702 metal oxide precursor Substances 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 238000007865 diluting Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910001960 metal nitrate Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 241000282376 Panthera tigris Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/02—Fixed-bed gasification of lump fuel
- C10J3/20—Apparatus; Plants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/18—Nitrates of ammonium
- C01C1/185—Preparation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/02—Oxides or hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/02—Magnesia
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide [Fe2O3]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0913—Carbonaceous raw material
- C10J2300/0916—Biomass
- C10J2300/092—Wood, cellulose
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0953—Gasifying agents
- C10J2300/0973—Water
- C10J2300/0976—Water as steam
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Fertilizers (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a method for comprehensively utilizing yellow phosphorus slag, which comprises the steps of adding the yellow phosphorus slag into nitric acid, stirring, reacting, centrifugally separating to obtain waste liquid and a white carbon black precursor, washing, drying, calcining, taking out, cooling and grinding to obtain a white carbon black product; uniformly mixing ammonia water and waste liquid, fully reacting, and then carrying out solid-liquid separation, wherein the obtained liquid is an ammonium nitrate solution, and concentrating and crystallizing to obtain a nitrogenous fertilizer; washing, drying and calcining the solid precipitate obtained by separation, cooling and grinding to obtain a nanoscale composite metal oxide product, and applying the nanoscale composite metal oxide to the field of biomass hydrogen production to improve the hydrogen yield; the invention uses waste yellow phosphorus slag as main raw material, so that the chemical industry solid waste is effectively and comprehensively utilized, and high-performance products are generated, thereby having great significance for comprehensive utilization of resources and environmental protection.
Description
Technical Field
The invention relates to the technical field of resource utilization, in particular to a method for comprehensively utilizing yellow phosphorus slag.
Background
Yellow phosphorus slag is an industrial solid waste discharged during yellow phosphorus production by an electrothermal method, a large amount of open-air stacking of the phosphorus slag not only occupies cultivated land, but also causes serious pollution to the environment because harmful elements such as fluorine, phosphorus and the like are gradually dissolved out under the leaching of rainwater. At present, the utilization of the phosphorus slag is mainly combined with the production of the cement industry, but when the phosphorus slag is added into the concrete as a mineral admixture, the early-stage pressure resistance of the concrete is reduced due to the existence of phosphate ions in the phosphorus slag. Therefore, a method for recycling yellow phosphorus slag is not easy to solve.
The process for producing the white carbon black mainly comprises the steps of forming hydrate by SiO 2, wherein the white carbon black is a porous substance, the composition of the white carbon black can be represented by SiO 2·nH2 O, and nH 2 O exists in the form of surface hydroxyl groups and can be dissolved in caustic alkali and hydrofluoric acid and is insoluble in water; white carbon black has excellent properties such as good reinforcing performance, high chemical stability, high temperature resistance, high dispersibility, high wear resistance, insulativity and the like, and can be widely applied to industries such as rubber, printing ink, papermaking, plastics, paint, dye, cosmetics and the like.
At present, the main method for industrially producing the precipitation method white carbon black is a sodium silicate acidification method, generally, sulfuric acid or hydrochloric acid is reacted with water glass, silicic acid is firstly generated, and then the generated silicic acid is further decomposed to prepare the white carbon black. However, the product prepared by the method has low activity, the size of the product particles is not easy to control, and the reinforcing performance is low. Patent application number 202111647850.7 discloses a process for by-producing precipitated white carbon black and light calcium carbonate by utilizing yellow phosphorus waste, but the process is complicated in the preparation process, and the process is not suitable for large-scale production.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention comprehensively utilizes yellow phosphorus slag, respectively prepares white carbon black, nano-scale composite metal oxide and nitrate fertilizer, the prepared nano-scale composite metal oxide is applied to the field of biomass hydrogen production, realizes high-value utilization of the yellow phosphorus slag, selects proper development and utilization directions according to the characteristics of each component part of the yellow phosphorus slag, and realizes clean and environment-friendly production of zero waste, zero waste liquid and zero waste gas in the production process.
The technical scheme of the invention is as follows:
a method for comprehensively utilizing yellow phosphorus slag comprises the following specific steps:
(1) Adding yellow phosphorus slag into nitric acid under the condition of continuous stirring, centrifuging after stirring reaction, carrying out solid-liquid separation to obtain waste liquid and a white carbon black precursor, washing the white carbon black precursor to a pH value of 5-7, drying, calcining, taking out, cooling and grinding to obtain a white carbon black product;
(2) Mixing ammonia water with the mass fraction of 5% -40% with the waste liquid in the step (1) according to the volume ratio of 4-10:1, fully reacting for 30-60 min after uniform mixing, and then realizing solid-liquid separation in a centrifuge, wherein the obtained liquid is an ammonium nitrate solution, and the nitrogen fertilizer is obtained after concentration and crystallization;
(3) Washing the solid precipitate obtained by the separation in the step (2) until the pH value is 11-13, drying, calcining, taking out, cooling and grinding to obtain the nano-scale composite metal oxide product.
The grain diameter of the yellow phosphorus slag in the step (1) is 100-250 mu m; the mass concentration of the nitric acid is 5-40%.
The yellow phosphorus slag in the step (1) is proportioned according to the mass ratio of nitric acid to the yellow phosphorus slag of 10-20:1 according to the amounts of different nitric acid concentrations.
The stirring reaction in the step (1) is carried out for 2 to 5 hours under the condition of continuously stirring at the temperature of 20 to 100 ℃.
When the solid-liquid separation is carried out by the centrifuges in the step (1) and the step (2), the rotating speed of the centrifuges is 3500-5000 r/min, and the centrifuging time is 15-20 min.
The drying temperature of the baking oven in the step (1) and the step (3) is 90-120 ℃, and the drying time of the baking oven is 12-24 hours.
The calcination temperature of the step (1) and the step (3) is 650-800 ℃ and the time is 1-2 h.
The nano-scale composite metal oxide product in the step (3) is used as a catalyst in biomass hydrogen production, and the specific method is as follows: mixing 60-80 g of nano-scale composite metal oxide and biomass according to the mass ratio of 1:1-5, placing the mixture into a furnace, heating the furnace to 600-800 ℃ at a constant heating rate of 15-20 ℃/min, and simultaneously introducing water vapor with the flow rate of 80-320 g/H to prepare hydrogen, wherein the concentration of H 2 can be measured by a gas concentration detector.
The biomass is wood, sugarcane, peanut shells, corn stalks and the like.
The invention has the technical effects that:
1. The method is simple, the characteristics of the components of the yellow phosphorus slag are fully combined to prepare a high-performance product, the utilization of the waste yellow phosphorus slag is improved, white carbon black, nano-scale composite metal oxide and nitrate fertilizer are respectively prepared, and the prepared nano-scale composite metal oxide is applied to the field of biomass hydrogen production and improves the hydrogen yield.
2. The invention realizes clean and environment-friendly production of zero waste, zero waste liquid and zero waste gas in the production process.
Drawings
FIG. 1 is a schematic diagram of the process flow for comprehensively utilizing waste yellow phosphorus slag.
Detailed Description
In order to make the technical scheme and advantages of the present invention more apparent, the present invention will be further described in detail with reference to the accompanying drawings and examples, but the scope of the present invention is not limited to the above. The yellow phosphorus slag used in the embodiment of the invention is taken from chemical industry limited company of Katsujingjiang tiger in Yunnan, and the yellow phosphorus slag is rich in metal elements such as calcium, silicon, aluminum, magnesium, iron and the like.
Example 1
A method for comprehensively utilizing yellow phosphorus slag is shown in fig. 1, and comprises the following steps:
(1) Diluting 100mL of 68% by mass of concentrated nitric acid with water to prepare a 20% by mass nitric acid solution, and grinding waste yellow phosphorus slag into powder with the particle size of 125 mu m in a grinder;
(2) Adding the nitric acid diluted in the step (1) into yellow phosphorus slag according to the mass ratio of the nitric acid to the yellow phosphorus slag of 10:1 under the condition of continuous stirring, continuously stirring at 100 ℃ for reaction for 4 hours, and centrifuging in a centrifuge at the rotating speed of 3500r/min for 20min to separate waste liquid and white carbon black precursors;
(3) Washing the white carbon black precursor in the step (2) with deionized water to a pH value of 7, drying at 120 ℃ for 12 hours, calcining at 750 ℃ for 1 hour, taking out, cooling, and grinding to obtain a white carbon black product, wherein the whiteness of the white carbon black product is 84.1%, and the purity is 98.8%;
(4) Mixing ammonia water with the mass concentration of 5% and the waste liquid in the step (2) according to the volume ratio of 4:1, fully reacting for 60min after completely mixing, centrifuging for 15min at the rotation speed of 5000r/min, and realizing solid-liquid separation in a centrifuge, wherein the obtained liquid is ammonium nitrate solution, and nitrogen fertilizer can be obtained through concentration and crystallization, and the obtained solid is a composite metal oxide precursor; (5) Washing the composite metal oxide precursor in the step (4) with deionized water to a pH value of 11, drying at 120 ℃ for 12 hours, calcining at 750 ℃ for 1 hour, taking out, cooling, and grinding to obtain a nanoscale composite metal oxide product, wherein the CaO content is 72.9%, the Al 2O3 content is 12.5%, the MgO content is 5.5%, and the Fe 2O3 content is 0.51%, and the balance is unavoidable impurities; (6) The prepared nano-scale composite metal oxide is applied to biomass hydrogen production, 80g of the nano-scale composite metal oxide is mixed with sugarcane according to the mass ratio of 1:4 and is put into a tube furnace, the furnace is heated to 700 ℃ at a constant heating rate of 15 ℃/min, water vapor with the flow rate of 160g/H is introduced in the reaction process, hydrogen is obtained, the proportion of H 2 in four gases H 2、CO、CO2、O2 is measured through a gas concentration detector, and the highest concentration of H 2 in the reaction process is 67.2%.
Comparative example 1
320G of sugarcane is put into a tube furnace, the furnace is heated to 700 ℃ at a constant heating rate of 15 ℃/min, during the reaction process, 160g/H of water vapor is introduced into the flow position to obtain hydrogen, and the proportion of H 2 in four gases H 2、CO、CO2、O2 is measured by a gas concentration detector, so that the highest concentration of H 2 in the reaction process is 23.2%.
From a comparison of example 1 and comparative example 1, it can be seen that the addition of the composite metal oxide prepared in example 1 can significantly improve the yield of hydrogen.
Example 2
A method for comprehensively utilizing yellow phosphorus slag comprises the following steps:
(1) Diluting 100mL of 68% by mass of concentrated nitric acid with water to prepare a 5% by mass nitric acid solution, and grinding waste yellow phosphorus slag into 100 mu m-diameter powder in a grinder;
(2) Adding the nitric acid diluted in the step (1) into yellow phosphorus slag according to the mass ratio of the nitric acid to the yellow phosphorus slag of 20:1 under the condition of continuous stirring, continuously stirring at 20 ℃ for reaction for 5 hours, and centrifuging in a centrifuge at the rotating speed of 5000r/min for 15min to separate waste liquid and white carbon black precursors;
(3) Washing the white carbon black precursor in the step (2) with deionized water until the pH value is 5, drying at 90 ℃ for 24 hours, calcining at 800 ℃ for 1 hour, taking out, cooling, and grinding to obtain a white carbon black product, wherein the whiteness of the white carbon black product is 80%, and the purity is 88%;
(4) Mixing ammonia water with the mass concentration of 40% and the waste liquid in the step (2) according to the volume ratio of 10:1, fully reacting for 30min after completely mixing, centrifuging for 20min at the rotating speed of 3500r/min, and realizing solid-liquid separation in a centrifuge, wherein the obtained liquid is ammonium nitrate solution, and nitrogen fertilizer can be obtained through concentration and crystallization, and the obtained solid is a composite metal oxide precursor;
(5) Washing the composite metal oxide precursor in the step (4) with deionized water to a pH value of 13, drying at 90 ℃ for 24 hours, calcining at 650 ℃ for 2 hours, taking out, cooling, and grinding to obtain a nanoscale composite metal oxide product, wherein the CaO content is 70.8%, the Al 2O3 content is 14.3%, the MgO content is 6.5%, and the Fe 2O3 content is 0.52%, and the balance is unavoidable impurities;
(6) The prepared nano-scale composite metal oxide is applied to biomass hydrogen production, 60g of heavy nano-scale composite metal oxide is mixed with sugarcane according to the mass ratio of 1:1 and is put into a tube furnace, the furnace is heated to 800 ℃ at a constant heating rate of 20 ℃/min, water vapor with the flow rate of 320g/H is introduced in the reaction process, hydrogen is obtained, the proportion of H 2 in four gases H 2、CO、CO2、O2 is measured by a gas concentration detector, and the highest concentration of H 2 in the reaction process is 66.8%.
Example 3
A method for comprehensively utilizing yellow phosphorus slag comprises the following steps:
(1) Diluting 100mL of 68% by mass of concentrated nitric acid with water to prepare a 20% by mass nitric acid solution, and grinding waste yellow phosphorus slag into powder with the particle size of 250 mu m in a grinder;
(2) Adding the nitric acid diluted in the step (1) into yellow phosphorus slag according to the mass ratio of the nitric acid to the yellow phosphorus slag of 15:1 under the condition of continuous stirring, continuously stirring at 60 ℃ for reaction for 3 hours, and centrifuging in a centrifuge at the rotating speed of 4000r/min for 18min to separate waste liquid and white carbon black precursors;
(3) Washing the white carbon black precursor in the step (2) with deionized water to a pH value of 6, drying at 100 ℃ for 15 hours, calcining at 800 ℃ for 1 hour, taking out, cooling, and grinding to obtain a white carbon black product, wherein the whiteness of the white carbon black product is 85%, and the purity is 90%;
(4) Mixing ammonia water with the mass concentration of 20% and the waste liquid in the step (2) according to the volume ratio of 5:1, fully reacting for 45min after completely mixing, centrifuging for 18min at the rotating speed of 4000r/min, and realizing solid-liquid separation in a centrifuge, wherein the obtained liquid is ammonium nitrate solution, and nitrogen fertilizer can be obtained through concentration and crystallization, and the obtained solid is a composite metal oxide precursor; (5) Washing the composite metal oxide precursor in the step (4) with deionized water to reach a pH value of 11, drying at 100 ℃ for 16 hours, calcining at 650 ℃ for 2 hours, taking out, cooling, and grinding to obtain a nanoscale composite metal oxide product, wherein the CaO content is 73.1%, the Al 2O3 content is 11.7%, the MgO content is 4.5%, and the Fe 2O3 content is 0.48%, and the balance is unavoidable impurities; (6) The prepared nano-scale composite metal oxide is applied to biomass hydrogen production, 70g of the nano-scale composite metal oxide and sugarcane are mixed according to the mass ratio of 1:2 and are placed into a tubular furnace, the furnace is heated to 600 ℃ at a constant heating rate of 18 ℃/min, 80g/H of water vapor is introduced in the reaction process to obtain hydrogen, the proportion of H 2 in four gases H 2、CO、CO2、O2 is measured through a gas concentration detector, and the highest concentration of H 2 in the reaction process is 63.2%.
Example 4
A method for comprehensively utilizing yellow phosphorus slag comprises the following steps:
(1) Diluting 100mL of 68% by mass of concentrated nitric acid with water to prepare 40% by mass of nitric acid solution, and grinding waste yellow phosphorus slag into powder with the particle size of 200 mu m in a grinder;
(2) Adding the nitric acid diluted in the step (1) into yellow phosphorus slag under the condition of continuously stirring according to the mass ratio of the nitric acid to the yellow phosphorus slag being 16:1, continuously stirring at 80 ℃ for reaction for 3 hours, and then centrifuging in a centrifuge at the rotating speed of 5000r/min for 15min to separate waste liquid and white carbon black precursors;
(3) Washing the white carbon black precursor in the step (2) with deionized water to a pH value of 7, drying at 90 ℃ for 24 hours, calcining at 650 ℃ for 2 hours, taking out, cooling, and grinding to obtain a white carbon black product, wherein the whiteness of the white carbon black product is 82%, and the purity is 89%;
(4) Mixing ammonia water with the mass concentration of 30% and the waste liquid in the step (2) according to the volume ratio of 4:1, fully reacting for 30min after completely mixing, centrifuging for 20min at the rotating speed of 3500r/min, and realizing solid-liquid separation in a centrifuge, wherein the obtained liquid is ammonium nitrate solution, and nitrogen fertilizer can be obtained through concentration and crystallization, and the obtained solid is a composite metal oxide precursor; (5) Washing the composite metal oxide precursor in the step (4) with deionized water to a pH value of 12, drying at 120 ℃ for 12 hours, calcining at 800 ℃ for 1 hour, taking out, cooling, and grinding to obtain a nanoscale composite metal oxide product, wherein CaO content is 75%, al 2O3 content is 13.8%, mgO content is 5.6% and Fe 2O3 content is 0.54%, and the balance is unavoidable impurities;
(6) The prepared nano-scale composite metal oxide is applied to biomass hydrogen production, 60g of the nano-scale composite metal oxide is mixed with sugarcane according to the mass ratio of 1:5 and is put into a tube furnace, the furnace is heated to 800 ℃ at a constant heating rate of 20 ℃/min, water vapor with the flow rate of 320g/H is introduced in the reaction process, hydrogen is obtained, the proportion of H 2 in four gases H 2、CO、CO2、O2 is measured through a gas concentration detector, and the highest concentration of H 2 in the reaction process is 57.2%.
The experiment is carried out by changing the biomass sugarcane into wood, peanut shells and corn stalks in the embodiment, and the highest concentration of H 2 in the reaction process is as follows: 43.3 to 55.8 percent, 49.8 to 62.7 percent and 40.5 to 53.8 percent, and the hydrogen production rate in the experimental process can be obtained: sugarcane is more than peanut shell is more than wood is more than corn straw.
The foregoing is only a partial, but not all embodiments of the present invention, and any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be covered by the scope of the claims of the present invention.
Claims (8)
1. A method for comprehensively utilizing yellow phosphorus slag is characterized by comprising the following specific steps:
(1) Under the condition of continuously stirring, adding yellow phosphorus slag into nitric acid, carrying out solid-liquid separation after stirring reaction to obtain waste liquid and a white carbon black precursor, washing the white carbon black precursor until the pH value is 5-7, drying, calcining, taking out, cooling and grinding to obtain a white carbon black product;
(2) Uniformly mixing ammonia water with mass fraction of 5% -40% with the waste liquid in the step (1) according to the volume ratio of 4-10:1, fully reacting for 30-60 min, and then carrying out solid-liquid separation, wherein the obtained liquid is an ammonium nitrate solution;
(3) Washing the solid precipitate obtained by the separation in the step (2) until the pH value is 11-13, drying, calcining, taking out, cooling and grinding to obtain a nanoscale composite metal oxide product;
the nano-scale composite metal oxide product is used as a catalyst in biomass hydrogen production, and the specific method is as follows: mixing 60-80 g of nano-scale composite metal oxide and biomass according to the mass ratio of 1:1-5, heating to 600-800 ℃ at the heating rate of 15-20 ℃/min, and simultaneously introducing water vapor with the flow rate of 80-320 g/h to prepare the hydrogen.
2. The method for comprehensively utilizing the yellow phosphorus slag according to claim 1, wherein the particle size of the yellow phosphorus slag in the step (1) is 100-250 μm; the mass fraction of the nitric acid is 5% -40%.
3. The method for comprehensively utilizing yellow phosphorus slag according to claim 1, wherein the mass ratio of nitric acid to yellow phosphorus slag in the step (1) is 10-20:1.
4. The method for comprehensively utilizing yellow phosphorus slag according to claim 1, wherein the stirring reaction in the step (1) is carried out at 20-100 ℃ for 2-5 hours.
5. The method for comprehensively utilizing yellow phosphorus slag according to claim 1, wherein the rotational speed of a centrifugal machine is 3500-5000 r/min and the centrifugal time is 15-20 min during solid-liquid separation in the step (1) and the step (2).
6. The method for comprehensively utilizing yellow phosphorus slag according to claim 1, wherein the drying temperature in the step (1) and the drying temperature in the step (3) are 90-120 ℃ and the drying time is 12-24 hours.
7. The method for comprehensively utilizing yellow phosphorus slag according to claim 1, wherein the calcining temperature in the step (1) and the calcining temperature in the step (3) are 650-800 ℃ and the calcining time is 1-2 h.
8. The method for comprehensively utilizing yellow phosphorus slag according to claim 1, wherein the biomass is wood, sugarcane, peanut shells or corn stalks.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2963434B1 (en) * | 1998-05-19 | 1999-10-18 | 品川白煉瓦株式会社 | Mold powder for continuous casting of steel |
| CN1903431A (en) * | 2006-08-01 | 2007-01-31 | 中国石油化工股份有限公司 | Composite catalyst used for reforming hydrogen prodn. using methane and water vapor as raw material, preparing process and use |
| CN102653393A (en) * | 2011-12-15 | 2012-09-05 | 北京金骄生物质化工有限公司 | Method for preparing hydrogen by utilizing waste biomass |
| CN103950911A (en) * | 2014-05-06 | 2014-07-30 | 云南磷化集团有限公司 | Method of preparing feed grade calcium hydrophosphate and co-producing water glass by using acid residues and yellow phosphorus slags |
| CN105349161A (en) * | 2015-11-06 | 2016-02-24 | 河北工业大学 | Method for producing hydrogen and carbon nanotubes through pyrolysis of waste tyres and biomass |
| CN106241883A (en) * | 2016-09-20 | 2016-12-21 | 四川大学 | The preparation method of ferrite |
| CN107902660A (en) * | 2017-10-25 | 2018-04-13 | 昆明理工大学 | A kind of yellow phosphorus furnace slag prepares SiO2The method of base ATO conductive powder materials |
| CN109675523A (en) * | 2018-12-19 | 2019-04-26 | 昆明理工大学 | A kind of yellow phosphorus furnace slag prepares the method and application of chromium adsorbent |
-
2023
- 2023-05-18 CN CN202310573712.1A patent/CN116588941B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2963434B1 (en) * | 1998-05-19 | 1999-10-18 | 品川白煉瓦株式会社 | Mold powder for continuous casting of steel |
| CN1903431A (en) * | 2006-08-01 | 2007-01-31 | 中国石油化工股份有限公司 | Composite catalyst used for reforming hydrogen prodn. using methane and water vapor as raw material, preparing process and use |
| CN102653393A (en) * | 2011-12-15 | 2012-09-05 | 北京金骄生物质化工有限公司 | Method for preparing hydrogen by utilizing waste biomass |
| CN103950911A (en) * | 2014-05-06 | 2014-07-30 | 云南磷化集团有限公司 | Method of preparing feed grade calcium hydrophosphate and co-producing water glass by using acid residues and yellow phosphorus slags |
| CN105349161A (en) * | 2015-11-06 | 2016-02-24 | 河北工业大学 | Method for producing hydrogen and carbon nanotubes through pyrolysis of waste tyres and biomass |
| CN106241883A (en) * | 2016-09-20 | 2016-12-21 | 四川大学 | The preparation method of ferrite |
| CN107902660A (en) * | 2017-10-25 | 2018-04-13 | 昆明理工大学 | A kind of yellow phosphorus furnace slag prepares SiO2The method of base ATO conductive powder materials |
| CN109675523A (en) * | 2018-12-19 | 2019-04-26 | 昆明理工大学 | A kind of yellow phosphorus furnace slag prepares the method and application of chromium adsorbent |
Non-Patent Citations (3)
| Title |
|---|
| Experimental Study of Purifying Precipitated Silica Produced from Yellow Phosphorus Slag;Li Guobing et al;Advanced Materials Research;20120124;第455-456卷;503-506 * |
| 韩长日等.《精细化工品实用生产技术手册》.科学技术文献出版社,1996,330. * |
| 黄磷渣制备改性白炭黑;程志飞等;应用化工;20170131;第46卷(第1期);90-95 * |
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